PSG has now claimed the prestigious trophy on fourteen different occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the match between the French league winners and the French Cup holders after the French winger found the net early on.
However, Marseille struck two times in the closing moments to seize a shock lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a crucial equaliser in the dying moments to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this competition for the 12th time in the past 13 years.
